Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 10 1 2010 10.5194/acpd-10-361-2010 http://www.atmos-chem-phys-discuss.net/10/361/2010/ http://www.atmos-chem-phys-discuss.net/10/361/2010/acpd-10-361-2010.html http://www.atmos-chem-phys-discuss.net/10/361/2010/acpd-10-361-2010.pdf 361 390 2010-01-08 In situ measurements of molecular iodine in the marine boundary layer: the link to macroalgae and the implications for O₃, IO, OIO and NO_x R.-J. Huang K. Seitz J. Buxmann D. Poehler K. E. Hornsby L. J. Carpenter U. Platt T. Hoffmann hoffmant@uni-mainz.de Institute for Inorganic and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10–14, 55128 Mainz, Germany Institute for Environmental Physics, University of Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg, Germany Department of Chemistry, University of York, Heslington, York YO10 5DD, UK "Single-point" in situ measurements of molecular iodine (I₂) were carried out in the coastal marine boundary layer (MBL) using diffusion denuders in combination with a gas chromatography-mass spectrometry (GC-MS) method. Comparison measurements were taken at Mace Head and Mweenish Bay, on the West Coast of Ireland. The observed mixing ratios of I₂ at Mweenish Bay are much higher than that at Mace Head, indicating the emissions of I₂ are correlated with the local algal biomass density and algae species. The concentration levels of I₂ were found to correlate inversely with tidal height and correlate positively with the concentration levels of O₃ in the surrounding air. However, the released I₂ can also lead to O₃ destruction via the reaction of O₃ with iodine atoms that are formed by the photolysis of I₂ during the day and via the reaction of I₂ with NO_x at night. IO and OIO were measured by long-path differential optical absorption spectroscopy (LP-DOAS). The results show that the concentrations of both daytime and nighttime IO are correlated with the mixing ratios of I₂. OIO was observed not only during the day but also, for the first time at both Mace Head and Mweenish Bay, at night. In addition, I₂ was measured simultaneously by the LP-DOAS technique and compared with the "single-point" in situ measurement. The results suggest that the local algae sources dominate the inorganic iodine chemistry at Mace Head and Mweenish Bay. 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